Tobacco product



United States Patent 3,331,691 TQBACQO PRQDUCT Joseph N. Schumacher andDonald L. Roberts, Winston- Salem, N.C., assignors to R. J. ReynoldsTobacco Company, Winston-Salem, N.C., a corporation of New ersey NoDrawing. Filed Nov. 8, 1965, Ser. No. 506,882 16 Claims. (Cl. 131-17)This invention relates to a tobacco product and has for an object theprovision of -a composition and process for improving the flavor andaroma of tobacco and tobacco smoke.

It is well known in the tobacco art that the flavor and aroma of thetobacco product and the smoke from the tobacco are very importantconsiderations in so far as the ultimate consumer is concerned.Considerable efforts are exerted by the manufacturers of tobaccoproducts .to provide a product that will be acceptable to the consumer,particularly as regards flavor and aroma characteristics. It has beenthe common practice in the tobacco industry to prepare blends ofdomestic and oriental tob accos in order to provide smoking tobaccowhich has a pleasing flavor and aroma before and during smoking.However, such a procedure is costly and may at times become prohibitivein the event that certain types of tobacco may be in short supply.Accordingly, it is a further object of this invention to provide a newclass of additive materials which when applied to the tobacco productsimprove and enhance the ilavor and aroma of these products and the smokeemitted therefrom, thereby increasing or enhancing the pleasure andother values that may be derived by the consumer from the use of theseproducts.

A further object of this invention is the provision of a process forenhancing or otherwise improving the flavor, aroma and other qualitiesof certain domestic, oriental, reconstituted or synthetic tobaccos whichmaybe deficient in said flavor or aroma or other qualities.

An additional object of this invention is to provide a process ofpreparing a smoking tobacco or product which when smoked has an enhancedflavor or aroma.

A still further object of this invention is the provision of smokingproducts, such as cigarettes, cigars or pipe tobacco, and a process forforming same whereby the flavor and aroma before and during smoking areimproved or enhanced.

Further and additional objects will appear from the followingdescription and the appended claims.

In accordance with one embodiment of this invention, a tobacco productis provided to which has been added or which has been treated with asmall amount of a com pound selected from the group having the formulae:

I II i w sh 0 OH COCHa CH3 N III IV 3,38L69l 'Patented May 7, 1968 H IIomo omomo 011(0113).

CH3CO CH=OHOO CH(CHa)2 VII EXAMPLE 1 A. Synthesis and properties of2,4-diphenylcrotonaldehyde (Formula I) The compound of Formula II is thecommercially available chemical diphenylether having a melting point of2627 and a nuclear magnetic resonance spectrum: T=2.70(l0).

EXAMPLE 3 A. Synthesis and Properties of2-acetonyl-4-methyltetrahydropyran (Formula III) (1) Preparation of2-hydroxy-4-methy1ltetrahydropyran.'Io a solution of 20 grams offi-methyl-5 valerolactone, commercially available, in 50 milliliters ofabs lute ether was added dI'OPlWlSC a solution of 1.67 grams of lithiumaluminum hydride in 50 milliliters of ether. After refluxing for anhour, the solution was hydrolyzed with water and the ether layer wasseparated from the aqueous layer. The aqueous layer was extracted twicemore with ether and the combined ether layers were dried and cncentrated, yielding 11.3 grams of 2-hydroxy-4-methyltetrahydropyran.

(2) 2-acetonyl-4-methyltetrahydropyran.2-hydroxy-4-methyltetrahydropyran (11.3 grams) was added dropwise to a stirredsolution of 36 milliliters of acetone, 36 milliliters of water and 3grams of a 30% sodium hydroxide solution. After stirring for six hours,the solution was allowed to stand 16 hours and then was neutralized with10% acetic a'cid. The aqueous layer was extracted several times withether and the residue from the ether layers was distilled, yielding 7.3grams of 2-acetonyl-4-methyltetra hydropyran, boiling point 56-63 C./ 1millimeter; nuclear magnetic resonance spectrum: 1:9.06 (3); 7.86(3);7.53 (2); and 637(2).

EXAMPLE 4 A. Synthesis and Properties of 2-methyl-5-isopropylpyridine(Formula IV) Ethyl 6-methylnicotinate, boiling point l13l6/ 11millimeters was prepared according to the method of P. A. Plattner, W.Keller and A. Boiler, Helv. Chim. Acta., 37, 1379-92 (1954). The ester,5.5 grams in 25 milliliters of ether, was added dropwise to 40milliliters of methylmagnesium bromide, 3 molar, in ethyl ether. Afterthe addition, the mixture was refluxed two hours and decomposed withpotassium hydroxide. The resulting layers were separated. The waterlayer was extracted with ether, and the ether extract was combined withthe organic layer, which was then dried over sodium sulphate. Removal ofthe solvent in vacuo yielded 4 grams of crude6-methylpyridine-5-dimethylcarbinol.

nuclear magnetic resonance spectrum: r=8.80(3); 870(3); 7.52(3);7.06(1); 260(1); and 165(1).

EXAMPLE A. Synthesis and properties of 6-methyl-2,5-heptanedione(Formula V) in a 500-milliliter 3-necked flask equipped with amagdissolved in 76 milliliters of absolute ether and placed in aSOD-milliliter 3-necked flask equipped with a magnetic stirring bar,reflux condenser, nitrogen inlet tube and a pressureequalizing additionfunnel. Isopropyl lithium (160 milliliters, 1.33 molar in pentane) wastransferred to the addition funnel under nitrogen pressure and addeddropwise over 1.5 hours. After an additional hour of stirring, water wasslowly and cautiously added. The organic layer that formed was separatedand the solvent removed in vacuo. The residue was mixed with 100milliliters of sulphuric acid and 60 milliliters of ethanol. Afterrefluxing /2 hour, the reaction mixture was diluted with water andextracted with ether. The ether extract was dried, the ether removed invacuo and the residue was distilled, yielding 14 grams of 6-methyl-2,5-heptanedione, boiling point 8889/ millimeters, nuclear magneticresonance spectrum: 1-:9.0(3); 888(3); 790(3); and 7.40(5).

EXAMPLE 6 A. Synthesis and properties of 6-rnethyl-3-heptene- 2,5-dione(Formula VI) A mixture of 10 grams of 6-methyl-2,S-heptanedione, 6 gramsof selenium dioxide, and 200 milliliters of water was warmed at 75 for12 hours. The mixture was filtered, and the filtrate was saturated withammonium sulphate and extracted with ether. The residue, after removingthe ether in vacuo, was distilled, yielding 5 grams of 6-methyl-3-heptene-2,5-dione, boiling point 98l00 C./2 millimeters;nuclear magnetic resonance spectrum: T=8.90(3); 878(3); 764(3); 7.10(1);and 313(2).

EXAMPLE 7 A. 6-methyl-5-hepten-2-ol (Formula VII) The compound6-methyl-5-hepten-2-ol is commercially available and has the followingproperties: boiling point 80 C./ millimeters; infrared spectrum: v=3300,1620, and 1115 cm. nuclear magnetic resonance spectrum: T=4.83(1,triplet), 6.15 (1, quadruplet), 7.92(2), 830(3), 837(3) and 8.83 (3,doublet); mass spectrum: parent peak at 128 mass units.

It has been found that the tobacco additives of the invention whenincorporated into tobacco products impart a flavor and arom both beforeand during smoking which many smokers consider to be desirable insmoking products. However, it is pointed out that the methods fordefining or characterizing the quality of a flavor or aroma in thetobacco art are almost purely subjective and different smokers maydefine the same flavor quite differently. Also, the compounds includedwithin the broad scope of this invention may impart different flavors oraromas depending upon the substituents therein. Thus, the compoundscomprehended by this invention, by subjective tests, impartcharacteristic flavors which are desirable in tobacco products and thesmoke therefrom even though the exact character thereof cannot bedescribed on the basis of known standards. The tobacco additive ofExample 1 imparts a sweet flowery aroma or flavor which is reminiscentof geraniums which many smokers consider to be desirable in a tobaccoproduct. The tobacco additive of Example 2 imparts an aroma which somecharacterize as similar to camphor-menthol; the tobacco additive ofExample 3 has a mild rose odor and imparts a banana-spicy aroma; thetobacco additive of Example 4 has an odor reminiscent of sweet potatoes;the compounds of Examples 5 and 6 impart a sweet taste; and the tobaccoadditive of Example 7 has a camphor note.

In accordance with this invention, an above indicated compound or amixture of compounds is added to tobacco or applied to a smoking articleor its component parts in amounts of about 0.0001 to 2.0 percent byweight of the product. However, the amount used will depend upon theamount of flavor and aroma desired and the particular compound ormixture thereof that is used. The additive may be incorporated at anystep in the treatment of the tobacco but is preferably added afteraging, curing and shredding and before the tobacco is formed intocigarettes. Likewise, it will be apparent that only a portion of thetobacco need be treated and the thus treated tobacco may be blended withother tobaccos before the cigarettes or other smoking articles areformed. In such case the tobacco treated may have the additive in excessof the amounts above indicated so that when blended with other tobaccosthe final product will have the percentage within the indicated range.

In accordance with one specific embodiment of this invention, an aged,flue-cured and shredded tobacco is sprayed with a 1% ethyl alcoholsolution of 2,4-diphenylcrotonaldehyde in an amount to provide a tobaccocontaining about 0.25 percent by weight of the additive on a dry basis.Thereafter the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. It has been foundthat the cigarette when prepared as indicated has a desired and pleasingflavor, an aroma which to some people is reminiscent of geranium and isdetectable and pleasing in the main and side smoke streams when thecigarette is smoked.

The additives falling within the scope of this invention may be appliedto the tobacco by spraying, dipping or otherwise, utilizing suitablesuspensions or solutions of the additive. Thus Water or volatile organicsolvents, such as alcohol, ether, acetone, volatile hydrocarbons and thelike. may be used as the carrying medium for the additive while it isbeing applied to the tobacco. Also, other flavorand aroma-producingadditives, such as those disclosed in United States Patents Nos.2,766,145, 2,905,575, 2,905,576, 2,978,365 and 3,041,211 may beincorporated into the tobacco with the .additive of this invention.

While this invention is principally useful in the manufacture ofcigarette tob acco, it is also suitable for use in connection with themanufacture of pipe tobacco, cigars or other tobacco products.Furthermore, the compounds may be added to certain tobacco substitutesof natural or synthetic origin and by the term tobacco as usedthroughout this specification is meant any composition intended forhuman consumption by smoking or otherwise, whether composed of tobaccoplant parts or substitute materials or both.

Also, the invention has been particularly described with reference tothe addition of the compounds directly to tobacco. However, it will beapparent that the compound may be applied to the paper of the cigaretteor to the wrapper of a cigar. Also, it may be incorporated into thefilter tip, the packaging material or the seam paste employed for gluingthe cigarette paper. Thus a tobacco product is provided which includesthe specified additives and tobacco although in every instance thecompound need not be admixed with the tobacco as above specificallydescribed.

While several particular embodiment of this invention are shown above,it will be understood, of course, that the invention is not to belimited thereto, since many modifications maybe made, and it iscontemplated, therefore, by the appended claims, to cover any suchmodifications as fall within the true spirit and scope of thisinvention.

We claim:

1. A tobacco product having added thereto an amount suificient to alterthe flavor or aroma of the tobacco product of a compound selected fromthe group 2,4-diphenylcrotonaldehyde, diphenylether,2-acetonyl-4-methyltetrahydropyran, 2-methyl-S-isopropylpyridine,6-methyl-2,5- heptanedione, 6-methyl-3heptene-2,5-dione, and6-methyl-5-hepten-2-ol.

2. The tobacco product recited in claim 1 wherein the amount of theflavoring compound is between about 0.0001 and 2.0 percent by weight ofthe product.

3. A tobacco product having added thereto a small amount suflicient toimprove the flavor thereof of 2,4- diphenylcrotonaldehyde.

4. The tobacco product recited in claim 3 wherein the flavoring additiveis present in an amount between about 0.0001 and 2.0 percent by weightof the product.

5. A tobacco product having added thereto a small amount suflicient toimprove the flavor thereof of diphenylether.

6. The tobacco product recited in claim 5 wherein the flavoring additiveis present in an amount between about 0.0001 and 2.0 percent by weightof the product.

7. A tobacco product having added thereto a small amount suflicient toimprove the flavor thereof of 2-acetonyl-4-methyltetrahydropyran.

8. The tobacco product recited in claim 7 wherein the flavoring additiveis present in an amount between about 0.0001 and 2.0 percent by weightof the product.

9. A tobacco product having added thereto a small amount sufficient toimprove the flavor thereof of Z-me-thyl-S-isopropylpyridine.

10. The tobacco product recited in claim 9 wherein the flavoringadditive is present in an amount between about 0.0001 and 2.0 percent byWeight of the product.

11. A tobacco product having added thereto a small amount sufficient toimprove the flavor thereof of 6-methyl-2,5-heptanedione.

12. The tobacco product recited in claim 11 wherein the flavoringadditive is present in an amount between about 0.0001 and 2.0 percent byweight of the product.

13. A tobacco product having added thereto a small amount suflicient toimprove the flavor thereof of 6-methyl-3-heptene-2,5-dione.

14. The tobacco product recited in claim 13 wherein the flavoringadditive is present in an amount between about 0.0001 and 2.0 percent byweight of the product.

15. A tobacco product having added thereto a small amount sufiicient toimprove the flavor thereof of 6-methyl-5-hepten-2-ol.

16. The tobacco product recited in claim 15 wherein the flavoringadditive is present in an amount between about 0.0001 and 2.0 percent byweight of the product.

References Cited UNITED STATES PATENTS 2,766,149 10/1956 Rowland 1317SAMUEL KOREN, Primary Examiner. D. J. DONOHUE, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,381,691 May 7 1968 Joseph N. Schumacher et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below: a

Column 3, line 11, afterl,06(l);" insert 2.96(1) line 16 cancel "in aSOO-milh liter. 3-necked flask equipffi with a mag-L and insert Ethyllevulinate ethylene glycol ketal (35 grams) was line 60, "arom" shouldread aroma Column 4 line 44, cancel the period and insert a comma.Column 6 line 28 '13- 17" should read 131 -17 Signed and sealed this23rd day of September 1969.

(SEAL) Allest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr,

Altesting Officer

1. A TOBACCO PRODUCT HAVING ADDED THERETO AN AMOUNT SUFFICIENT TO ALTERTHE FLAVOR OR AROMA OF THE TOBACCO PRODUCT OF A COMPOUND SLECTED FROMTHE GROUP 2,4-DIPHENYLCROTONALDEHYDE, DIPHENYLETHER,2-ACETONYL-4-METHYLTE RAHYDROPYRAN, 2-METHYL-5-ISOPROPYLPYRIDINE,6-METHYL-2,5HEPTANEDIONE, 6-METHYL-3-HEPTENE-2,5-DIONE, AND6-METHYL-5-HEPTEN-2-OL.